Core-extended perylene bisimides

ABSTRACT

The present inventions relates to nucleus-extended perylenebisimides of formula (I)intermediates in the preparation of compounds (I) and processes for the preparation of those intermediates and also processes for the preparation of compounds, (I), and the use thereof as colorants.

This application is a 371 of PCT/EP99/07814 filed Oct. 11, 1999, now WO00/23446.

The present invention relates to nucleus-extended perylenebisimides ofgeneral formulae (I) and (II)

wherein

R¹ and R² are each independently of the other unsubstituted orsubstituted C₁-C₂₄alkyl, C₁-C₂₄cycloalkyl, or C₆-C₁₀aryl, and

A¹ and A³ are each independently of the other —S—, —S—S—, —CH═CH—,R³OOC—C(—)═C(—)—COOR³, —N═N— or —N(R⁴)—, or a linkage selected from thegroup consisting of the organic radicals of formulae (III), (IV), (V),(VI) and (VII)

wherein

R³ is hydrogen, C₁-C₂₄alkyl or C₁-C₂₄cycloalkyl,

R⁴ is unsubstituted or substituted C₁-C₂₄alkyl, C₁-C₂₄cycloalkyl,phenyl, benzyl, —CO—C₁—C₄alkyl, —CO—C₆H₅ or C₁-C₄alkylcarboxylic acid(C₁-C₄alkyl) ester, and

A² is a linkage of formula (III), (IV) or (V),

also to intermediates for the preparation of compounds (I) and (II) andto processes for the preparation of those intermediates and also toprocesses for the preparation of compounds (I) and (II), and to the usethereof as colourants.

Perylenes, as is known (see Heterocycles, Vol. 40, No. 1, (1995)477-500), are photostable fluorescent dyes that are often distinguishedby high fluorescence quantum yields. A disadvantage thereof is, however,that perylenes have a low degree of solubility in aqueous media.

Chem. Ztg. (1975), 99, 92-93 describes, inter alia, nucleus-extendedperylenes that are obtainable by Diels-Alder reaction of4-phenyl-1,2,4-triazoline-3,5-dione with perylene and that may exhibitabsorptions at 600 nm.

Further Diels-Alder reactions on perylenes are described inHeterocycles, Vol. 40, No. 1, 1995. J. Org. Chem. USSR, (1986), 22,943-946 describes the preparation of thio- and dithio-cyclic derivativesof perylene-3,4,9,10-tetracarboxylic acid. Furthermore, J. Org. Chem.USSR, (1980), 16, 762-7 describes a process for the preparation ofnitrogen-cyclic derivatives of perylene-3,4,9,10-tetracarboxylic acid.

The problem underlying the invention was accordingly to provide furthernucleus-extended perylenes, especially nucleus-extendedperylenebisimides, that preferably as fluorescent dyes have goodfastness to heat and to light; perylenes suitable as NIR dyes or asfluorescent markers were also to be provided.

Accordingly, there have been found the nucleus-extendedperylenebisimides of general formulae (I) and (II) defined at thebeginning.

C₁-C₂₄Alkyl is, for example, methyl, ethyl, n- or iso-propyl, n-, iso-,sec- or tert-butyl, n- or neo-pentyl, n-hexyl, n-heptyl, n-octyl,n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl,n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl,n-eicosyl, heneicosyl, docosyl or tetracosl, preferably1-(C₁-C₉alkyl)-C₂-C₁₀alkyl, such as 1-methyl-ethyl, 1-ethyl-n-propyl,1-n-propyl-n-butyl, 1-n-butyl-n-pentyl, 1-n-hexyl-1-n-heptyl,1-n-heptyl-1-n-octyl, 1-n-octyl-1-n-nonyl or 1-n-nonyl-1-n-decyl, orC₁-C₈alkyl, such as methyl, ethyl, n- or iso-propyl, n-, iso-, sec- ortert-butyl, n- or neo-pentyl, n-hexyl, n-heptyl or n-octyl andespecially C_(1 -C) ₄alkyl, such as methyl, ethyl, n- or iso-propyl orn-, iso-, sec- or tert-butyl.

C₃-C₁₄Cycloalkyl is, for example, cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl,cycloundecyl, cyclododecyl, cyclotridecyl or cyclotetradecyl, preferablyC₅-C₈cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl orcyclooctyl.

Especially preferred compounds of formulae (I) and (II) are thosewherein R₁ and/or R₂ denote a secondary alkyl radical, such as1-(C₁-C₉alkyl)-C₂-C₁₀alkyl, especially those wherein the radical R₁has aso-called “swallowtail structure”, such as 1-methyl-ethyl,1-ethyl-n-propyl, 1-n-propyl-n-butyl, 1-n-butyl-n-pentyl,1-n-hexyl-1-heptyl, 1-n-heptyl-1-n-octyl, 1-n-octyl-1-n-nonyl,1-n-nonyl-1-decyl, or an aromatic radical, especially the phenylradical, very especially C₁-C₆alkyl-substituted phenyl, such as2,6-di-tert-butylphenyl and 2,5-di-tert-butylphenyl.

C₆-C₁₀Aryl is, for example, phenyl or 1- or 2-naphthyl, especiallyphenyl.

—CO—C₁-C4Alkyl is —CO-methyl, —CO-ethyl, —CO-n-propyl, —CO-isopropyl, or—CO-n-, —CO-iso-, —CO-sec- or —CO-tert-butyl.

C₁-C₄Alkylcarboxylic acid (C₁-C₄alkyl) ester is, for example,methylcarboxylic acid methyl ester, methylcarboxylic acid ethyl ester,methylcarboxylic acid n-propyl ester, methylcarboxylic acid isopropylester, methylcarboxylic acid n-butyl ester or methylcarboxylic acidisobutyl ester, methylcarboxylic acid sec-butyl ester ormethylcarboxylic acid tert-butyl ester or ethylcarboxylic acid methylester, ethylcarboxylic acid ethyl ester, ethylcarboxylic acid n-propylester, ethylcarboxylic acid isopropyl ester, ethylcarboxylic acidn-butyl ester, ethylcarboxylic acid sec-butyl ester or ethylcarboxylicacid tert-butyl ester, n-propylcarboxylic acid methyl ester orn-butylcarboxylic acid methyl ester.

Hal is, for example, halide and denotes fluoride, chloride, bromide oriodide.

Especially preferred perylene-3,4:9,10-tetracarboxylic acid bisimides ofgeneral formulae (I) and (II) are those wherein R¹ and R² are eachindependently of the other 1-n-hexyl-1-heptyl, 2,5-di-tert-butylphenyl,1-nonyl-1-decyl or 1-n-butyl-n-pentyl; very especially R² is R¹.

Very special preference is given to perylene-3,4:9,10-tetracarboxylicacid bisimides of general formulae (I) and (II) wherein A¹ is —S—, NR⁴,—CH═CH—, R³OOC—C(−) ═C(−)—COOR³, or a linkage of formula (III), (IV),(V), (VI) or (VII) and A² and A³ are an organic radical of formula (V)or A² and A³ are each independently of the other an organic radical offormula (III), (IV) or (V).

Preferred perylenes of the present invention are the compounds offormulae (VIII) to (XX) given below, wherein R¹ and R² are especiallyeach independently of the other 1-hexyl-1-heptyl,2,5-di-tert-butylphenyl, 1-nonyl-1-decyl or 1-butyl-pentyl,

very especially R¹ and R² in (VII) are 1-n-hexyl-1-heptyl,2,5-di-tert-butylphenyl or 1-butylpentyl, and

wherein very especially R¹ and R ² are 1-n-hexyl-1-heptyl, and

wherein preferably

R⁴ is unsubstituted or substituted C₁-C₂₄alkyl, C₁-C₂₄cycloalkyl,phenyl, and especially cyclohexyl or 2,5-di-tert-butylphenyl, and

R¹ and R² are very especially 1-n-hexyl-1-heptyl, and

wherein

R¹ and R² are very especially 1-n-hexyl-1-heptyl, and

wherein

R¹ and R² are very especially 1-n-hexyl-1-heptyl, and

wherein

R¹ and R² are very especially 1-n-hexyl-1-heptyl,2,5-di-tert-butylphenyl or 1-n-butyl-n-pentyl, and

wherein preferably

R⁴ is unsubstituted or substituted C₁-C₂₄alkyl, phenyl, benzyl,—CO—C₁-C₄alkyl, —CO—C₆H₅ or C₁-C₄alkylcarboxylic acid (C₁-C₄alkyl)ester, and especially C₁-C₄alkyl, more especially methyl, benzyl,—CH₂COOC₂H₅, —COCH₃ or —CO-phenyl, and

R¹ and R² are very especially 1-n-hexyl-1-heptyl,2,5-di-tert-butylphenyl or 1-n-butyl-n-pentyl, and

wherein

R¹ and R² are very especially 1-n-hexyl-1-heptyl,2,5-di-tert-butylphenyl or 1-n-butyl-n-pentyl, and

wherein

R¹ and R² are very especially 1-n-hexyl-1-heptyl,2,5-di-tert-butylphenyl or 1-n-butyl-n-pentyl, and

wherein especially

R⁴ is substituted or unsubstituted phenyl, and

R¹ and R² are very especially 1-n-hexyl-1-heptyl, and

wherein preferably

R³ is C₁-C₄alkyl, especially methyl or ethyl, and

R¹ and R² are very especially 1-n-hexyl-1-heptyl, and

wherein

R¹ and R² are very especially 1-n-hexyl-1-heptyl, and

wherein especially

R⁴ is phenyl, and

R¹ and R² are very especially 1-n-hexyl-1-heptyl, and

wherein especially

R⁴ is phenyl, and

R1 and R² are very especially 1-n-hexyl-1-heptyl.

The perylenebisimides (I) according to the invention wherein A¹ is A⁴,wherein A⁴ is a linkage selected from the group consisting of theorganic radicals of formulae (III), (IV), (V) and (VII), andperylenebisimides (II) wherein A² is A⁵, wherein A⁵ is a linkage offormula (III) or (V), and A¹ is A⁶, wherein A⁶ is a linkage of formula(V), are preferably obtained by Diels-Alder reactions, as described inJ.Chem.Soc. (1957), 96, 5616-4619.

The present invention accordingly relates also to a process for thepreparation of perylenebisimides (I) wherein A¹ is A⁴, wherein A⁴ is alinkage selected from the group consisting of the organic radicals offormulae (III), (IV), (V), (VII) and —N═N—, by Diels-Alder reaction of adiene with a dienophile at elevated temperature, wherein there arereacted, as diene, a perylenebisimide of formula (XXI)

and, as dienophile, a compound selected from the group consisting of thecompounds of formulae (XXII), (XXIII) and (XXIV)

The order in which the starting materials (XXI) and (XXII), (XXI) and(XXIIa), or (XXI) and (XXIII), or (XXI) and (XXIV), are added is notgenerally important. It has, however, proved to be advantageous to use acompound of formula (XXII), (XXIIa), (XXIII) or (XXIV) as the initialcharge and then to add the compound (XXI).

The compounds of formulae (XXII), (XXIIa), (XXIII) and (XXIV) aregenerally used in excess, preferably in a molar ratio of compounds(XXII):(XXI), (XXIIa):(XXI), (XXIII):(XXI) or (XXIV):(XXI) in the rangeof from 1.1:1 to 20:1, especially from 1.3:1 to 15:1.

The reaction is preferably carried out at a reaction temperatures in therange of from 80 to 200° C., especially from 100 to 150° C. According toobservations hitherto, the success of the reaction is not dependent uponthe pressure range selected. For simplicity's sake, the reaction iscustomarily carried out at atmospheric pressure, but it is also possibleto select pressures in the range of from 10 kPa to 10 MPa. The reactiontimes are selected, depending on the reaction temperature chosen,preferably in the range of from 1 hour to 4 weeks, especially in therange of from one day to 4 weeks.

It has proved advantageous to carry out the reaction in the presence ofan organic solvent. As solvent there come into consideration, forexample, dipolar aprotic solvents, such as acetonitrile, benzonitrile,N,N′-dimethylformamide, N,N′-dimethylacetamide, nitrobenzene,N-methylpyrrolidone, aliphatic hydrocarbons, which may if desired behalogenated, such as trichloroethane, dichloroethane, trichloromethaneor dichloromethane, or cycloalkanes, such as cyclohexane orcycloheptane, or aromatic hydrocarbons or mixtures thereof, such asbenzine (as a mixture of different, essentially aliphatic hydrocarbons),or unsubstituted or alkyl-, alkoxy- or halo-substituted benzene, such astoluene, xylene, anisole or chlorobenzene, and also ethers, such astetrahydrofuran, dioxane or EtOCH₂CH₂OH (e.g. in the form of Cellosolve®commercially available from Fluka) or glycol ethers, such as ethyleneglycol methyl ether, ethylene glycol ethyl ether, diethylene glycolmonomethyl ether or diethylene glycol monoethyl ether, ornitrogen-containing solvents, such as pyridine, triethylamine, picolineor quinoline, and keto-group-containing solvents, such as acetone ormethyl ethyl ketone. The above-mentioned solvents may also be used inthe form of mixtures with one another.

The weight ratio of solvent to the sum of the reactants is customarilyin the range of from 0.001 to 20% by weight, preferably from 0.001 to10% by weight.

In an especially preferred embodiment of the process according to theinvention, a compound of formula (XXII), (XXIIa), (XXIII) or (XXIV),preferably of formula (XXII), is reacted with a compound (XXI).

In a further preferred embodiment, the reaction is carried out in aprotective gas atmosphere. Preferred protective gases are, for example,nitrogen and the noble gases, such as helium or argon.

It has also proved to be extremely advantageous to carry out the processaccording to the invention in the presence of an oxidising agent, forexample para-chloranil, in order to rearomatise the addition product.

The perylenebisimides of formula (XXI) are known or can be preparedaccording to known methods as described in Heterocycles (1995), 40,477-500, for example by reacting a perylenebisanhydride with a primaryamine to form a perylenebisimide.

The present invention relates also to a process for the preparation ofperylenebisimides (II) wherein A² is an organic radical of formula(III), (IV) or (V) and A¹ is (V), by Diels-Alder reaction of a dienewith a dienophile at elevated temperature, wherein a perylenebisimide offormula (XXI) is reacted with a compound of formula (XXII), (XXIIa),(XXIII), or (XXIV), or perylenebisimides of formula (XVI) are reactedwith compounds of formula (XXII), (XXIIa) or (XXIII).

The reaction parameters generally correspond to those in the Diels-Alderreaction described above.

The compounds of formulae (XXII), (XXIIa), (XXIII) and (XXIV) aregenerally used in excess, preferably in a molar ratio of the compounds((XXII) or (XXIIa) or (XXIII) or XXIV)):((XXI) or (XVI)) in a range offrom 2.1:1 to 50:1, especially from 1.3:1 to 15:1.

The order in which the starting materials (XXI), (XXII), (XXIIa),(XXIII) or (XXIV) are added is generally not important. It has, however,proved advantageous to use the compound of formula (XXI) as the initialcharge and then to add the compounds (XXII), (XXIIa), (XXIII) or (XXIV).

The perylenebisimides (I) and (II) prepared according to the Diels-Alderreactions according to the invention can be purified and isolated inaccordance with customary methods, such as by chromatography, especiallycolumn chromatography, or crystallisation, especially extractiverecrystallisation (e.g. analogously to the method described in Chem.Ber. 118 (1985) 4641-4645)).

Generally the perylenebisimides (I) and (II) can be used afterpurification and isolation directly for further reactions.

The present invention accordingly relates also to a process for thepreparation of perylenebisimides of formula (IXa), (IXb) or (X), whereinthe compound of formula (VII) is reacted with

a) NH₃ or amidosulfuric acid, or

b) a primary amine of formula (XXV) H₂N—R⁴, or

c) a primary diamine of formula (XXVI)

The amine (XXV) or (XXVI) or NH₃ or amidosulfuric acid is generally usedin excess, preferably in a molar ratio of the perylenebisimide (I) to(XXV) or (XXVI) or NH₃ or amidosulfuric acid in a range of from 1:1.1 to1:20, especially in the range of from 1:1.3 to 1:15.

The reaction is preferably carried out at reaction temperatures in therange of from 80 to 200° C. According to observations hitherto, thesuccess of the reaction is not dependent upon the pressure rangeselected. For simplicity's sake, the reaction is customarily carried outat atmospheric pressure, but it is also possible to select pressures inthe range of from 10 kPa to 10 MPa. The reaction times are selected,depending on the reaction temperature chosen, preferably in the range offrom 1 hour to 40 hours, especially in the range of from 2 hours to 25hours.

It has proved advantageous to carry out the reaction in the presence ofan organic solvent. As solvent there come into consideration, forexample, those mentioned above. Special preference is given tonitrogen-containing solvents, especially quinoline, and halogenatedaliphatic hydrocarbons, such as trichloromethane.

The weight ratio of the sum of the reactants to the solvent iscustomarily in the range of from 100 to 0.001% by weight, preferablyfrom 50:0.001% by weight.

A preferred embodiment of the process according to the invention relatesto the reaction in the presence of N,N′-dicyclohexylcarbodiimide (DCC)in trichloromethane.

An especially preferred embodiment of the process according to theinvention relates to the reaction in the presence ofN,N′-dicyclohexylcarbodiimide (DCC) and trifluoroacetic acid intrichloromethane.

The molar ratio of DCC to the compound (VII) is customarily in the rangeof from 20:1 to 1:1, preferably from 15:1 to 1:1 and very especially inthe range of from 10:1 to 1:1.

The molar ratio of trifluoroacetic acid to the compound (VIII) iscustomarily in the range of from 0.0001:100 to 0.1:10.

In a preferred embodiment, the reaction is carried out in a protectivegas atmosphere. Preferred protective gases are, for example, nitrogenand the noble gases, such as helium or argon.

It has also been found that the compound (VII) can be converted into adicarboxylic acid derivative (XXVIIa)

and by esterification into the dicarboxylic acid ester of formula(XXVIIb)

wherein R⁵ is C₁-C₂₄alkyl or C₁-C₂₄cycloalkyl.

A further embodiment of the present invention accordingly relates alsoto a process for the preparation of compounds of formula (XXVIIa) byhydrolysis of an anhydride, wherein the compound (VIII) is used asanhydride and is reacted with an acid or a base, preferably in anaqueous medium.

The hydrolysis of anhydrides is known and is described, for example, inSurvey of Organic Syntheses, by Calvin A. Buehler and Donald E. Pearson,Wiley-Interscience, USA, (1970).

The reaction is preferably carried out at reaction temperatures in therange of from −10 to 200° C., especially from 0 to 150° C. According toobservations hitherto, the success of the reaction is not dependent onthe pressure range selected. For simplicity's sake, the reaction iscustomarily carried out at atmospheric pressure, but it is also possibleto select pressures in the range of from 10 kPa to 10 MPa. The reactiontimes are selected, depending on the reaction temperature chosen,preferably in the range of from 1 hour to 24 hours.

As acid there may be used, for example, an inorganic acid, such ashydrochloric acid, sulfuric acid, Lewis acids, such as borontrifluoride, or organic acids, such as methanesulfonic acids, formicacid or para-toluenesulfonic acid.

As bases there may be used, for example, alkali metal alcoholates, suchas sodium or potassium methanolate or sodium or potassium ethanolate,and alkali metal carbonates and alkali metal hydrogen carbonates, suchas sodium carbonate or potassium carbonate, and sodium hydrogencarbonate or potassium hydrogen carbonate, and alkali metal hydroxides,such as sodium hydroxide, potassium hydroxide, especially potassiumhydroxide powder (85% by weight potassium hydroxide and 15% by weightwater), and also lithium aluminium hydride, potassium tert-butanolate,triethylamine, aluminium alkanolate and also non-nucleophilic bases,such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU),1,5-diazabicyclo[4.3.0]non-5-ene ((DBN) orN,N,N′,N′-tetramethylethylenediamine (TMEDA).

The acid or base is generally used in a molar ratio of acid or base tocompound (VIII) in the range of from 0.1:1 to 20:1.

It has proved advantageous to carry out the reaction in the presence ofan organic solvent. As solvent there come into consideration, forexample, those mentioned above.

The weight ratio of the sum of the reactants to the solvent iscustomarily in the range of from 0.001 to 20% by weight, preferably from0.001 to 10% by weight.

In a further preferred embodiment, the reaction is carried out in aprotective gas atmosphere. Preferred protective gases are, for example,nitrogen and the noble gases, such as helium or argon.

The present invention relates also to a process for the preparation ofdiester derivatives (XXVIIb) by esterification of a dicarboxylic acid,wherein a compound of formula (XXVIIa) is reacted with an alcohol offormula (XXVIII), HO-R⁵, or with an alkyl halide of formula (XXIX),Hal-R⁵, in the presence of an acid or a base.

Suitable bases and acids are those mentioned above.

Methods for the esterification of carboxylic acids are known anddescribed, for example, in Survey of Organic Synthesis, (1970).

A particular embodiment of the process according to the inventionrelates to the reaction with a base. Non-nucleophilic bases inparticular have proved to be advantageous.

Generally the molar ratio of base to compound (XVIIa) is in the range offrom 100:1 to 1:100, preferably in the range of from 20:1 to 1:20.

The molar ratio of alkyl halide to base is generally in the range offrom 5:1 to 1:5, preferably in the range of from 2:1 to 1:2.

It has proved advantageous to carry out the reaction according to theinvention in the presence of solvents. Suitable solvents are thosementioned above.

Generally the solvent is used in an amount sufficient to dissolve thecompound (XVIIa).

It has also been found that the dicarboxylic acid derivatives (XVIIa)and anhydrides of formula (VII) can be decarboxylated.

The present invention accordingly relates also to a process for thepreparation of perylenebisimides of formula (XI), by decarboxylation ofa dicarboxylic acid or an anhydride with copper or a copper-containingcompound, wherein a compound of formula (XXVIIa) or (VIII) is reacted inthe presence of a solvent.

The decarboxylation of carboxylic acids can, as is known, be carried outwith copper in the presence of quinoline (see Survey of OrganicSynthesis, (1970), 144, 145 ).

Copper denotes, for example, copper powder, and as copper-containingcompound there can be used copper(I) or copper(II) salts, preferablycopper(I) or copper(II) oxide, copper chromite or copper sulfate; it ispreferred to use copper powder.

Copper or a copper-containing compound is generally used in excess. Themolar ratio of copper (or copper equivalent in copper-containingcompounds) to the compound of formula (XVIIa) or (VIII) is preferably inthe range of from 1.1:1 to 20:1, especially in the range of from 1.3:1to 15:1.

The reaction is preferably carried out at reaction temperatures in therange of from 80 to 200° C., especially from 120 to 180° C. According toobservations hitherto, the success of the reaction is not dependent onthe pressure range selected. For simplicity's sake, the reaction iscustomarily carried out at atmospheric pressure, but it is also possibleto select pressures in the range of from 10 kPa to 10 MPa. The reactiontimes are selected, depending on the reaction temperature chosen,preferably in the range of from 1 hour to 48 hours, especially in therange of from 1 hour to 10 hours.

It has proved advantageous to carry out the reaction in the presence ofan organic solvent. As solvent there come into consideration, forexample, those mentioned above for the process for the preparation ofthe compound of formula (VII). Especially preferred solvents arenitrogen-containing solvents, with special preference being given toquinoline and 3-picoline.

The weight ratio of the sum of the reactants to the solvent iscustomarily in the range of from 0.001 to 20% by weight, preferably from0.001 to 10% by weight.

In a further preferred embodiment, the reaction is carried out in aprotective gas atmosphere. Preferred protective gases are, for example,nitrogen and the noble gases, such as helium or argon.

The present invention relates also to perylenebisimides of formula (XXX)and to perylene monoanhydride-monoimides of formula (XXXI)

wherein

R⁷ and R⁸ are each independently of the other hydrogen, NO₂,PO(OR¹¹)(OR¹²), Br, NH₂ or N(R¹¹R²)₂, wherein

R¹¹ and R¹² are each independently of the other a radical mentionedunder R², and R⁹ and R¹⁰ are each independently of the other hydrogen,NO₂, NH₂ or N(R¹¹R²)₂.

Special preference is given to substituted perylenebisimides of formulae(XXXII) to (XXXIX), wherein especially R¹ and R² are each independentlyof the other 1-n-hexyl-1-heptyl, 2,5-di-tert-butylphenyl,1-nonyl-1-decyl or 1-n-butyl-n-pentyl,

and wherein preferably

R¹² and R¹¹ are unsubstituted or substituted C₁-C₄alkyl, especiallymethyl or ethyl, and wherein R¹ and R² are very especially1-hexyl-1-heptyl or 1-butyl-pentyl, and

and

wherein R¹ and R² are very especially 1-hexyl-1-heptyl,2,5-di-tert-butylphenyl or 1-butylpentyl, and

and

wherein R¹ and R² are very especially 1-hexyl-1-heptyl, and

wherein R¹ and R2 are very especially 1-hexyl-1-heptyl or1-butyl-pentyl, and

wherein R¹ and R 2 are very especially 1-hexyl-1-heptyl or1-butyl-pentyl, and

wherein preferably

R¹¹ and R³ are unsubstituted or substituted C₁-C₄alkyl, especiallymethyl or ethyl, and

wherein R¹ is very especially 1-hexyl-1-heptyl or 1-butyl-pentyl, and

wherein R¹ is very especially 1-hexyl-1-heptyl or 1-butyl-pentyl.

Perylene monoanhydride-monoimides can be used as starting compounds inthe preparation of perylenebisimides in close analogy to known methods.For example, Heterocycles (1995), 40, 477-500 describes how anhydridederivatives of perylenes can be reacted with primary amines to form thecorresponding imides.

The anhydride derivatives according to the invention can also be used asfluorescent markers.

The nitro derivatives, especially monosubstituted derivatives, ofderivatives of perylenetetracarboxylic acid have hitherto beenobtainable only in unsatisfactory yields (see, for example, J. Org.Chem. USSR (Engl. Translation) 1980, 16, 762-766).

It has now been found that perylenebisimides of formula (XXI) andperylene monoanhydride-monoimides of formula (XXXI) wherein R⁹ and R¹⁰are hydrogen can be substituted by a single nitro group in good yields.

The present invention accordingly relates also to a process for thepreparation of compounds of formulae (XXXIII), (XXXVIII) and (XXXIX),wherein compounds of formula (XXI) or (XXXI) wherein R⁹ and R¹⁰ arehydrogen are reacted with N₂O₄ in the presence of a solvent.

The reaction is preferably carried out at reaction temperatures in therange of from −10 to 40° C., especially from 0 to 25° C. According toobservations hitherto, the success of the reaction is not dependent onthe pressure range selected. For simplicity's sake, the reaction iscustomarily carried out at atmospheric pressure, but it is also possibleto select pressures in the range of from 10 kPa to 10 MPa. The reactiontimes are selected, depending on the reaction temperature chosen,preferably in the range of from 1 hour to 24 hours, especially in therange of from 2 hours to 10 hours.

The molar ratio of N₂O₄ to the compounds of formula (XXI) is customarilyin the range of from 0.5:1 to 2:1, preferably from 0.8:1 to 1.5:1.

The molar ratio of N₂O₄ to the compounds of formula (XXXI) wherein R⁹and R¹⁰ are hydrogen is customarily in the range of from 0.5:1 to 4:1,preferably from 0.8:1 to 1.5:1.

It has proved advantageous to carry out the reaction in the presence ofan organic solvent. As solvents there come into consideration, forexample, those solvents mentioned above for the process for thepreparation of perylenebisimides (I) wherein A¹ is A⁴. Especiallypreferred solvents are halogenated aliphatic hydrocarbons, such asespecially dichloromethane.

A particular embodiment of the process according to the inventionrelates to the reaction in the presence of a catalyst.

As catalyst there are used, for example, acids, such as sulfonic acids,trifluoroacetic acid, trifluoromethanesulfonic acid, methanesulfonicacid or toluenesulfonic acid, preferably methanesulfonic acid.

The molar ratio of catalyst to the compound of formula (XXI) or (XXXI)wherein R⁹ and R¹⁰ are hydrogen is customarily in the range of from0.0001:1 to 1:1.

The molar ratio of solvent to the compound of formula (XXI) or (XXXI)wherein R⁹ and R¹⁰ are hydrogen is generally in the range of from 0.01:1to 100:1, preferably from 0.1:1 to 50:1.

In a further preferred embodiment, the reaction is carried out in aprotective gas atmosphere. Preferred protective gases are, for example,nitrogen and the noble gases, such as helium or argon.

The compounds (XXXIII), (XXXVIII) and (XXXIX) prepared according to thenitration processes according to the invention can be purified andisolated according to customary methods, such as by chromatography,especially column chromatography, or crystallisation, especiallyextractive recrystallisation.

It has also been found that the nitro derivatives of formulae (XXXIII),(XXXVIII) and (XXXIX) can be converted to their amino derivatives byreduction.

The present invention accordingly relates also to a process for thepreparation of compounds of formulae (XXXVa), (XXXVIa) and (XXXVIIa)wherein perylenebisimides of formulae (XXXIII), (XXXVIII) and (XXXIX)are reacted

a) with iron in the presence of an acid, or

b) with palladium in the presence of hydride transporters such astriethylamine/formic acid or triethylammonium formate, hydrazine orderivatives thereof, or phosphinic or phosphoric acid.

For example, it is known from Survey of Organic Syntheses, by Calvin A.Buehler and Donald E. Pearson, Wiley-Interscience, USA, (1970), 413 to417, that nitro compounds can be reduced with iron under acid conditionsor with palladium/carbon and hydrogen. Furthermore, reduction withpalladium is described, in the presence of formic acid, in J. Chem. Soc.Perkin Trans,I, (1977), 443, and in the presence of triethylammoniumformate, in J.Org.Chem.(1977), 42,3491.

The reaction is preferably carried out at reaction temperatures in therange of from −10 to 150° C., especially from 0 to 100° C. According toobservations hitherto, the success of the reaction is not dependent uponthe pressure range selected. For simplicity's sake, the reaction iscustomarily carried out at atmospheric pressure, but it is also possibleto select pressures in the range of from 10 kPa to 10 MPa. The reactiontimes are selected, depending on the reaction temperature chosen,preferably in the range of from 5 minutes to 24 hours, especially in therange of from 5 minutes to 5 hours, very especially from 5 minutes to 2hours.

As acid there is customarily used an inorganic or organic acid.Preference is generally given to the use of an inorganic acid, forexample hydrochloric acid, especially concentrated hydrochloric acid.

The molar ratio of iron to (XXXIII), (XXXVIII) and (XXXIX) iscustomarily in the range of from 1:10 to 15:1, preferably from 1:1 to10:1.

The weight ratio of acid to iron is generally in the range of from0.001:1 to 100:1.

It has proved advantageous to carry out the reaction in the presence ofan organic solvent. As solvent there come into consideration, forexample, those listed above for the process for the preparation ofperylenebisimides (I) wherein A¹ is A⁴.

The weight ratio of (XXXIII), (XXXVIII) or (XXXIX) to the solvent usedis customarily in the range of from 0.001 to 100% by weight, preferablyfrom 0.001 to 20% by weight.

In a preferred embodiment of the process according to the invention, ithas proved advantageous to use palladium/carbon instead of palladium.

The weight ratio of palladium/carbon (with 5% by weight palladium basedon carbon) to (XXXIII), (XXXVIII) and (XXXIX) is generally in the rangeof from 0.01:1 to 1:1, preferably in the range of from 0.1:1 to 0.5:1and very especially in the range of from 0.1:1 to 0.3:1.

The molar ratio of triethylamine to formic acid is customarily in therange of from 1:0.1 to 0.9:1, preferably in the region of 1:0.5 andespecially in the region of 1:0.7.

The molar ratio of triethylamine or triethylammonium formate to(XXXIII), (XXXVIII) and (XXXIX) is customarily in the range of from 5:1to 100:1.

In a further preferred embodiment, the reaction is carried out in aprotective gas atmosphere. Preferred protective gases are, for example,nitrogen and the noble gases, such as helium or argon.

The amino derivatives (XLII) and (XLIII) prepared according to theprocesses of the invention can be purified and isolated in accordancewith customary methods, such as by chromatography, especially columnchromatography, or crystallisation, especially extractiverecrystallisation.

The present invention relates also to a process for the preparation ofcompounds of formulae (XXXV), (XXXVI) and (XXXVII), wherein thecompounds of formula (XXXVa) or (XXXVla) and (XXXVIIa) are reacted witha base with alkyl halides of formula R'¹¹-Hal and/or R³-Hal, wherein Halis fluoride, chloride, bromide, iodide and R¹¹ and R³ are eachindependently of the other hydrogen or C₁-C₂₄alkyl, C₁-C₂₄cycloalkyl,and R¹¹ and R³ are preferably the same. Houben-Weyl, Methoden derOrganischen Chemie, G. Thieme Verlag Stuttgart, 1957, 4^(th) ed., Vol.11, Pt, 1., Chap. 2 describes methods for alkylating amines.

The reaction is preferably carried out at reaction temperatures in therange of from −10 to 150° C., especially from 0 to 50° C., veryespecially from 0 to 30° C. According to observations hitherto, thesuccess of the reaction is not dependent on the pressure range selected.For simplicity's sake, the reaction is customarily carried out atatmospheric pressure, but it is also possible to select pressures in therange of from 10 kPa to 10 MPa. The reaction times are selected,depending on the reaction temperature chosen, preferably in the range offrom 1 hour to 48 hours.

As base there is customarily used an inorganic base, such as, forexample, an alkali metal hydroxide, such as potassium hydroxide, sodiumhydroxide, or an alkali metal carbonate, such as sodium carbonate,potassium carbonate, or an alkali metal hydrogen carbonate, such assodium hydrogen carbonate or potassium hydrogen carbonate. It has provedespecially advantageous to use aqueous potassium hydroxide. The weightratio of potassium hydroxide to water is generally in the range of from0.0001:1 to 1:1.

The molar ratio of the base to the amino derivatives of formula (XXXVa)or (XXXVla) and (XXXVIIa) is customarily in the range of from 1:10 to10:1, preferably from 1:5 to 5:1.

The molar ratio of R¹¹-Hal to R³-Hal is generally in the range of from1:100 to 100:1.

It has proved advantageous to carry out the reaction in the presence ofan organic solvent. As solvent there come into consideration, forexample, those solvents listed above in the process for the preparationof perylenebisimides (I) wherein A¹ is A⁴.

The weight ratio of the sum of the reactants to the solvent iscustomarily in the range of from 0.001 to 100% by weight, preferablyfrom 0.001 to 20% by weight.

A special development of the present reaction relates to the use ofdipolar aprotic solvents.

It has proved especially advantageous to carry out the reaction in thepresence of a dipolar aprotic solvent and a phase-transfer catalyst.

As phase-transfer catalyst there may be used, for example,triethylbenzylammonium chloride or triethylbenzylammonium bromide.

The molar ratio of phase-transfer catalyst to (XXXVa) or (XXXVIa) and(XXXVIIa) is customarily in the range of from 0.0001:1 to 0.8:1,preferably from 0.001:1 to 0.5:1.

In a further preferred embodiment, the reaction is carried out in aprotective gas atmosphere. Preferred protective gases are, for example,nitrogen and the noble gases, such as helium or argon.

The present invention accordingly relates also to a process for thepreparation of compounds of formulae (XXXV) or (XXXVI) and (XXXVII)wherein R¹¹ and R³ are alkyl, preferably methyl, wherein the compound offormula (XXXVa) or (XXXVIa) and (XXXVIIa) is reacted with HCHO or with aformaldehyde-providing compound in the presence of formic acid(Leuckart-Wallach reaction) and a solvent, or alkylated with an alkyliodide and a phase-transfer catalyst, preferably methyl iodide inaqueous potassium hydroxide solution and triethylammonium chloride.

The reaction is preferably carried out at reaction temperatures in therange of from −10 to 200° C. According to observations hitherto, thesuccess of the reaction is not dependent on the pressure range selected.For simplicity's sake, the reaction is customarily carried out atatmospheric pressure, but it is also possible to select pressures in therange of from 10 kPa to 10 MPa. The reaction times are selected,depending on the reaction temperature chosen, preferably in the range offrom 1 hour to 48 hours.

As formaldehyde-providing compound there may be used, for example,paraformaldehyde or trioxane. Formaldehyde can be used in the form of agas or in the form of a formalin solution.

The molar ratio of formic acid to the compound of formula (XXXVa) or(XXXVIa) and (XXXVIIa) is customarily in the range of from 1:100 to100:1.

The concentration of the formalin solution is generally from 35 to 37per cent by weight.

The molar ratio of the formalin solution to the compounds of formulae(XXXVa) or (XXXVIa) and (XXXVI1a) is customarily in the range of from1:1 to 100:1.

It has proved advantageous to carry out the reaction in the presence ofan organic solvent. As solvent there come into consideration, forexample, those solvents listed above for the process for the preparationof perylenebisimides (I) wherein A¹ is A⁴. Particularly advantageous assolvent are N,N′-dimethylformamide, N,N′-dimethylacetamide, nitrobenzeneand N-methylpyrrolidone.

The weight ratio of the compounds of formulae (XXXVa) or (XXXVIa) and(XXXVIIa) to the solvent is customarily selected in the range of from0.001 to 100% by weight, preferably from 0.001 to 20% by weight.

A special development of the present reaction relates to the use ofdipolar aprotic solvents.

As phase-transfer catalyst there may be used, for example,triethylbenzylammonium chloride or triethylbenzylammonium bromide.

The molar ratio of phase-transfer catalyst to compounds of formulae(XXXVa) or (XXXVIa) and (XXXVIIa) is customarily in the range of from0.0001:1 to 0.8:1, preferably from 0.001:1 to 0.5:1.

In a further preferred embodiment, the reaction is carried out in aprotective gas atmosphere. Preferred protective gases are, for example,nitrogen and the noble gases, such as helium or argon.

The reaction product is preferably isolated by precipitation with waterand subsequent filtration.

It has proved advantageous to adjust the precipitated reaction productin water to a pH value in the range of from 7.5 to 10 with a base.

As base there may be used, for example, sodium hydroxide, potassiumhydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate or potassium hydrogen carbonate.

The compounds of formulae (XXXVa) or (XXXVIa) and (XXXVIIa) isolatedaccording to the processes of the invention can be purified inaccordance with customary methods, such as by chromatography, especiallycolumn chromatography, or crystallisation, especially extractiverecrystallisation.

In the present invention it has also been found that trialkylphosphonatederivatives (XXXII) and pyrrolo derivatives (XII) can be obtained fromthe above nitro derivatives of the compounds of formula (XXXIII) byreaction with trialkyl phosphite.

The present invention accordingly relates also to a process for thepreparation of perylenebisimide trialkylphosphonates of formula (XXXII)and perylenebisimide pyrroles of formula (XII), wherein the compound offormula (XXXIII) is reacted with trialkyl phosphite of the formula P(OR¹²(OR¹¹)(OR⁵) wherein R¹², R¹¹ and R⁵ are as defined above and areespecially C₁-C₄ alkyl.

Synthesis 1969, 11 to 17, describes methods for the reaction of amineswith trialkyl phosphite, so that further details on the subject aresuperfluous.

The reaction is preferably carried out at reaction temperatures in therange of from −10 to 150° C., especially from 100 to 150° C. Accordingto observations hitherto, the success of the reaction is not dependenton the pressure range selected. For simplicity's sake, the reaction iscustomarily carried out at atmospheric pressure, but it is also possibleto select pressures in the range of from 10 kPa to 10 MPa. The reactiontimes are selected, depending on the reaction temperature chosen,preferably in the range of from 1 hour to 48 hours.

The molar ratio of the nitro derivative (XXXIII) to the trialkylphosphite is customarily in the range of from 1:1 to 1:500, preferablyfrom 1:10 to 1:200.

It has proved advantageous to carry out the reaction in the presence ofan organic solvent. As solvent there come into consideration, forexample, those solvents listed above for the process for the preparationof perylenebisimides (I) wherein A¹ is A⁴.

The weight ratio of nitro derivative (XXXIII) to solvent is customarilyselected in the range of from 1 to 100% by weight.

In a further preferred embodiment, the reaction is carried out in aprotective gas atmosphere. Preferred protective gases are, for example,nitrogen and the noble gases, such as helium or argon.

The pyrrolo and trialkylphosphonate derivatives of formulae (XXXII) and(XII) prepared according to the process of the invention can be purifiedand isolated in accordance with customary methods, such as bychromatography, especially column chromatography, or crystallisation,especially extractive recrystallisation.

It has proved especially advantageous to separate and purify the pyrroloand trialkylphosphonate derivatives of formulae (XXXII) and (XII) bycolumn chromatography using trichloromethane as eluant on aluminiumoxide.

It has also been found that the pyrrolo derivatives of formula (XII) canbe alkylated, benzylated or acylated.

The invention accordingly relates also to a process for the preparationof compounds of formula (XIII), wherein a compound of formula (XII) isreacted with a halide of formula R⁴-Hal, in the presence of a base.

The reaction is preferably carried out at reaction temperatures in therange of from -10 to 100° C., especially from 0 to 50° C., veryespecially from 0 to 30° C. According to observations hitherto, thesuccess of the reaction is not dependent on the pressure range selected.For simplicity's sake, the reaction is customarily carried out atatmospheric pressure, but it is also possible to select pressures in therange of from 10 kPa to 10 MPa. The reaction times are selected,depending on the reaction temperature chosen, preferably in the range offrom 1 hour to 48 hours.

As bases there may be used the bases listed above for the process forthe preparation of compounds of formula (XXVII).

The molar ratio of base to pyrrolo derivatives of formula (XII) iscustomarily in the range of from 1:10 to 10:1, preferably from 1:5 to5:1.

In a preferred embodiment of the process according to the invention, thereaction of a pyrrolo derivative of formula (XII) with a halide iscarried out in the presence of a solvent.

A particular embodiment of the process according to the inventionrelates to the reaction in the presence of potassium hydroxide powder inthe presence of a protic solvent. For example, alcohols, such asmethanol, ethanol, propanol, isopropanol, n-, sec- or tert- butanol, n-,sec- or tert-pentanol, have proved to be especially advantageous asprotic solvents.

In a further particular embodiment of the process according to theinvention, there are used generally non-nucleophilic bases, such as1,8-diazabicyclo[5.4.0]undec-7-ene (DBU),1,5-diazabicyclo[4.3.0]non-5-ene ((DBN) orN,N,N′,N′-tetramethylethylenediamine (TMEDA).

It has proved advantageous to carry out the reaction in the presence ofan organic solvent. As solvent there come into consideration, forexample, the solvents listed above for the process for the preparationof perylenebisimides (I) wherein A¹ is A⁴. Special preference is givento N,N′-dimethylformamide, N,N′-dimethylacetamide or N-methylpyrrolidoneand to trichloroethane, dichloroethane, trichloromethane ordichloromethane; ethers are especially preferred, with specialpreference being given to tetrahydrofuran.

The weight ratio of pyrrolo derivative (XII) to solvent is customarilyin the range of from 0.001 to 100% by weight, preferably from 0.001 to20% by weight.

The pyrrolo compound derivatives isolated according to the processes ofthe invention can be purified in accordance with customary methods, suchas by chromatography, especially column chromatography, orcrystallisation, especially extractive recrystallisation.

It has also been found in the present invention that theperylenebisimides of formula (XXXIII) are suitable for thenucleus-extension of perylenebisimides with sulfur.

The present invention accordingly relates also to a process for thepreparation of compounds of formulae (XIV) and (XV), wherein1-nitro-perylenebisimides of formula (XXXIII) are reacted with sulfur inthe presence of a solvent.

The reaction is preferably carried out at reaction temperatures in therange of from −10 to 200° C., especially from 0 to 150° C. According toobservations hitherto, the success of the reaction is not dependent onthe pressure range selected. For simplicity's sake, the reaction iscustomarily carried out at atmospheric pressure, but it is also possibleto select pressures in the range of from 10 kPa to 10 MPa. The reactiontimes are selected, depending on the reaction temperature chosen,preferably in the range of from 1 hour to 40 hours, especially in therange of from 5 hours to 24 hours.

It has proved advantageous to carry out the reaction in the presence ofan organic solvent. As solvent there come into consideration, forexample, the solvents listed above for the process for the preparationof perylenebisimides (I) wherein A¹ is A⁴. Special preference is givento dipolar aprotic solvents, such as N,N′-dimethylformamide,N,N′-dimethylacetamide, nitrobenzene and N-methylpyrrolidone.

The weight ratio of solvent to the 1-nitroperylenebisimide of formula(XXXIII) is customarily in the range of from 1:1 to 1000:1, preferablyfrom 1:10 to 500:1.

The molar ratio of sulfur to the 1-nitroperylenebisimide (XXXIII) iscustomarily in the range of from 10:0.1 to 0.9:1, preferably in therange of from 5:0.1 to 4:1.

In a further preferred embodiment, the reaction is carried out in aprotective gas atmosphere. Preferred protective gases are, for example,nitrogen and the noble gases, such as helium or argon.

It has proved advantageous to treat the reaction mixture with dilutemineral acid, such as hydrochloric acid, at a temperature in the rangeof from 80 to 120° C., especially from 90 to 110° C., the desiredproduct being precipitated.

If desired, the resulting precipitate can be washed with water and, ifdesired, the precipitate can be dried.

Furthermore, the precipitate, which may or may not have been dried, canbe purified in accordance with customary methods, such as bychromatography, especially column chromatography, or crystallisation,especially extractive recrystallisation.

A further embodiment of the present invention relates to the use of theperylenes (I), (II), (XXX) and (XXXI) according to the invention ascolourants, especially as pigments and dyes, in each case in accordancewith methods generally known per se, preferably

(a) for melt colouration of polymers, it being possible to use aspolymers polyvinyl chloride, cellulose acetate, polycarbonate,polyamide, polyurethane, polyimide, polybenzimidazole, melamine resin,silicone, polyester, polyether, polystyrene, polymethyl methacrylate,polyethylene, polypropylene, polyvinyl acetate, polyacrylonitrile,polybutadiene, polychlorobutadiene or polyisoprene, and the copolymersof the mentioned monomers;

(b) as vat dyes or mordant dyes, for example for dyeing naturalmaterials and, especially, paper, wood, straw, leather, animal skins ornatural fibre materials, such as cotton, wool, silk, jute, sisal, hemp,flax or animal hair (e.g. horsehair) and their conversion products, suchas viscose fibres, nitrocellulose silk or copper rayon, preferred saltsfor mordanting being aluminium, chromium and iron salts;

(c) in the manufacture of paints, lacquers, especially automotivelacquers, coating compositions, paper dyes, printing inks, inks,especially for use in ink-jet printers, preferably in homogeneoussolution as fluorescent inks, and for drawing and writing purposes, andin electrophotography, for example for dry-copying systems (Xeroxprocess) and laser printers;

(d) for security-marking purposes, such as for cheques, cheque cards,bank notes, coupons, documents, identity papers and the like, where aparticular, unmistakable colour impression is to be achieved;

(e) as an additive to colourants, such as pigments and dyes, in which aparticular shade of colour is to be achieved; especially luminescentshades are preferred;

(f) for labelling objects for the purpose of mechanically recognisingthose objects by means of fluorescence, preference being given to themechanical recognition of objects for sorting, for example for therecycling of plastics, with alpha-numerical printing or bar codespreferably being used;

(g) for frequency conversion of light, for example in order to makelonger-wavelength, visible light from short-wavelength light, or forfrequency doubling or frequency tripling of laser light in non-linearoptics;

(h) for the production of passive display elements for a wide variety ofdisplay, information and labelling purposes, for example passive displayelements, road signs and traffic signals, such as traffic lights;

(i) as starting material for supraconducting organic materials (via π-πinteractions, after doping with, for example, iodine there is usuallyobtained an intermediate charge delocalisation);

(j) for fluorescent labelling of solids;

(k) for decorative and artistic purposes;

(I) for tracer purposes, for example in biochemistry, medicine,technology and natural science, it being possible to link the colourantsaccording to the invention covalently to substrates or via secondaryvalences, such as hydrogen bonds or hydrophobic interactions(adsorption); examples thereof are protein-dye combinations,antibody-dye combinations or DNA- or RNA-dye combinations,

(m) as fluorescent dyes in highly sensitive detection methods (see C.Aubert, J. Fünfschilling, 1. Zschokke-Gränacher and H. Langhals, Z.Analyt. Chem. 1985, 320, 361), especially as fluorescent dyes inscintillators;

(n) as dyes or fluorescent dyes in optical light-collecting systems, influorescent quantum counters, in fluorescent solar collectors (see H.Langhals, Nachr. Chem. Tech. Lab. 1980, 28, 716), influorescence-activated displays (see W. Greubel and G. Baur, Elektronik1977, 26, 6), in cold-light sources for light-induced polymerisation inthe preparation of plastics, for materials' testing, for example in themanufacture of semiconductor circuitry, for the investigation ofmicrostructures of integrated semiconductor components, inphotoconductors, in photographic processes, in display, illumination orimage-converting systems in which excitation is effected by means ofelectrons, ions or UV radiation, for example in fluorescent displays,Braun tubes or in fluorescent tubes, as part of an integratedsemiconductor circuit, which contain dyes as such or in conjunction withother semiconductors, for example in the form of an epitaxy, inchemiluminescent systems, for example in chemiluminescent light rods, inluminescent immunoassays or other luminescent detection methods, ashighlighter inks, especially for lending visual prominence to text anddrawings or other graphic products, for identifying signs and otherobjects where a particular visual colour impression is to be achieved,in dye lasers, preferably as fluorescent dyes for producing laser beamsand as Q-switches;

(o) as rheology improvers and

(p) for modifying inorganic solids, such as aluminium oxide, siliconoxide, for example, in zeolite cages, titanium dioxide, tin oxide,magnesium oxide (“xylolith”), silicates, clay minerals, chalk-, gypsum-or cement-containing surfaces such as paints or plaster surfaces inwhich the free carboxyl function provides special adhesion to thesurface, or

(q) as NIR dyes for information technologies.

In particular, the compounds wherein R₁ and/or R₂ is/are 1-butyl-pentyl,1-hexyl-1-heptyl, 1-heptyl-1-octyl, 1-octyl-1-nonyl, 1-nonyl-1-decyl and2,5-di-tert-butylphenyl are distinguished by their good solubility.

EXAMPLES Example 1a 1-Nitro-N,N′-bis(1-butylpentyl)perylene-3,4:9,10-bis(dicarboximide) (XL)

N,N′-Bis(1-butylpentyl)perylene-3,4:9,10-bis(dicarboximide) (prepared asdescribed in Chem. Ber. 1988, 121, 225-230) 2.00 g (3.12 mmol), 30 ml ofdichloromethane, a solution of N₂O₄ in dichloromethane, 37 ml (0.085molar, 3.15 mmol, prepared as described below) and methanesulfonic acid,0.02 ml (0.30 mmol), are reacted at 25° C. for 6 hours. The reactionmixture is concentrated to about 2 ml. The residue is taken up in 10 mlof toluene and worked up by chromatography on silica gel/toluene. Yield2.1 g (98%) (XL) in the form of a dark-red powder, m.p. 304° C., R_(f)(silica gel/toluene): 0.31.

Example 1b1-Nitro-N,N′-bis(1-hexylheptyl)perylene-3,4:9,10-bis(dicarboximide)(XLI)

N,N′-Bis(1-hexylheptyl)perylene-3,4:9,10-bis(dicarboximide) (prepared asdescribed in Chem. Ber. 1988, 121, 225-230), 2.07 g (2.75 mmol), asolution of N₂O₄ in dichloromethane, 14.0 ml (0.198 molar, 2.77 mmolN₂O₄/prepared as described below), and methanesulfonic acid, 0.05 ml(0.77 mmol), are reacted at 25° C. for 7 hours. The reaction mixture isconcentrated to about 2 ml. The residue is taken up in 10 ml of tolueneand worked up by chromatography on silica gel/toluene. Yield 2.04 g(93%) (XLI) dark-red powder, m.p. 121° C., R_(f) (silicagel/trichloromethane): 0.84. - R_(f) (silica gel/toluene): 0.63.

Example 1c 1-Nitro-N,N′-bis(2,5-di-tert-butylphenyl)perylene-3,4:9,10-bis(dicarboximide)(XLII)

N,N′-bis(2,5-di-tert-butylphenyl)perylene-3,4:9,10-bis(dicarboximide)(prepared as described in Chem. Ber. 1985, 118, 4641-4645), 800 mg (1.04mmol), dichloromethane, 30 ml, a solution of N₂O₄ in dichloromethane, 21ml (0.05 molar,1.05 mmol, prepared as described below), andmethanesulfonic acid, 0.05 ml (0.77 mmol), are reacted at 25° C. for 4hours. The crude product is concentrated to about 1 ml. The residue istaken up in 10 ml of trichloromethane and worked up by chromatography onsilica gel/trichloromethane. Yield: 800 mg (94%)(XLII) dark-redcrystalline powder, m.p.>300° C., R_(f) (silica gel/trichloromethane):0.45.

Example 1d 1-Nitro-N-(1-hexylheptyl)-perylene-3,4:9,10-tetracarboxylicacid 3,4-anhydride-9, 10-imide (XLIII) and12-nitro-N-(1-hexylheptyl)-perylene-3,4:9,10-tetracarboxylic acid3,4-anhydride-9, 10-imide (XLIV)

N-(1-Hexylheptyl)-perylene-3,4:9,10-tetracarboxylic acid3,4-anhydride-9, 10-imide, 100 mg (0.175 mmol) (prepared as described inChem. Ber. 124, 529-535), dichloromethane, 50 ml, a solution of N₂O₄ indichloromethane 5.5 ml (0.03 molar, 0.165 mmol, prepared as describedbelow), and methanesulfonic acid, 0.05 ml (0.77 mmol), are reacted at25° C. for 4 hours. The crude product is concentrated to about 1 ml. Theresidue is taken up in 20 ml of trichloromethane and worked up bychromatography on silica gel/trichloromethane/7% glacial acetic acid.Yield: 83 mg (77%) of a mixture of (XLIII) and (XLIV) in the form of adark-red powder, m.p.: 189-191° C., R_(f) (silica gel/dichloromethane/2% glacial acetic acid): 0.73.

Preparation of an N₂O₄ solution: Pb(NO₃)₂ is heated for a few minutes atfrom 250 to 600° C. and the N₂O₄ gas that is released is introduced intodichloromethane until saturated. To determine the concentration of thesolution of N₂O₄ in dichloromethane, 10 ml of the solution are shakentogether with 10 ml of 30% by weight hydrogen peroxide until thelight-brown colour disappears. The result is a two-phase mixture. Thelower dichloromethane phase is separated off. The upper aqueous phase istitrated against NaOH (0.1N) using phenolphthalein as indicator todetermine the nitric acid content.

Example 2aN,N′-Bis(1-hexylheptyl)perylene-3,4:9,10-bis(dicarboximide)-1-diethylphosphonate(XLV) andN,N′-bis(1-hexylheptyl)pyrrolo[2,3,4,5-hik]perylene-3,4:8,9-bis(dicarboximide)(XLVI)

(XLI), prepared analogously to Example 1b, 150 mg (0.188 mmol) andtriethyl phosphite, 5 ml (29.1mmol), are reacted under an argonatmosphere at 130° C. for 5 hours. The reaction mixture is then reactedwith 1N hydrochloric acid, 150 ml, at about 25° C. for about 12 hours,to yield a dark-red precipitate. The precipitate is filtered off withsuction and dried. For further purification, the precipitate is taken upin trichloromethane and worked up by chromatography on aluminiumoxide/trichloromethane:

1st fraction: yield 43 mg (26%) (XLV), m.p. 61-63° C., R_(f) (Al₂O₃/trichloromethane): 0.82

2nd fraction: yield 91 mg (63%) (XLVI), m.p. 204-205° C., R_(f) (Al₂O₃/trichloromethane): 0.42.

Example 2bN,N′-Bis(1-butylpentyl)perylene-3,4:9,10-bis(dicarboximide)-1-diethylphosphonate(XLVII) andN,N′-bis(1-butylpentyl)pyrrolo[2,3,4,5-hik]perylene-3,4;8,9-bis(dicarboximide)(XLVIII)

(XL), prepared analogously to Example 1a, 300 mg (0.437 mmol) andtriethyl phosphite, 10 ml (9.69 g, 58.3 mmol), are reacted under anargon atmosphere at 130° C. for 3 hours. The reaction mixture is thenprovided with 1N hydrochloric acid, 100 ml, and reacted at about 25° C.for about 12 hours to yield a dark-red precipitate. The precipitate isfiltered off with suction and dried. For further purification, theprecipitate is taken up in trichloromethane and worked up bychromatography on aluminium oxide (activity levelII)/-trichloromethane/1% ethanol:

1st fraction: yield 109 mg (32%) (XLVII), m.p. 122-124° C., R_(f)(Al₂O₃/trichloromethane): 0.62.

fraction: yield 160 mg (56%) (XLVIII), m.p.>300° C., R_(f) (Al₂O₃,neutral/trichloromethane): 0.24.

Example 3N,N″-Bis(1-butylpentyl)-N′-methyl-pyrrolo[2,3,4,5-hik]perylene-3,4;8,9-bis(dicarboximide)(XLIX) Method A

(XLVIII), prepared analogously to Example 2b, 100 mg (0.153 mmol),ethanol, 10 ml, and potassium hydroxide powder, 17 mg (0.258 mmol), arereacted with iodomethane, 0.5 ml (8 mmol) at about 25° C. for about 12hours. The ethanol is then distilled off. The residue of the reactionmixture is taken up in trichloromethane and washed several times withwater. The organic solvent phase is then dried with magnesium sulfateand subsequently concentrated to dryness. The residue is taken up intrichloromethane and worked up by chromatography on silicagel/trichloromethane: Yield 93 mg (91%) (XLIX) cherry-red powder.

Method B: (XLVIII), 100 mg (0.153 mmol) and ethanol, 10 ml, are reactedwith potassium hydroxide powder, 17.0 mg (0.258 mmol). The resultingviolet solution is concentrated, and the residue is taken up inN-methylpyrrolidone and reacted with iodomethane, 0.1 ml (1.6 mmol) ) at25° C. for 12 hours. The reaction mixture is then poured into water, andsufficient ethanol is added for the N-methylpyrrolidone to dissolve, andstirring is carried out at 25° C. for 12 hours. The ethanol is thendistilled off. The residue of the reaction mixture is taken up intrichloromethane and washed several times with water. The organicsolvent phase is then dried with magnesium sulfate and subsequentlyconcentrated to dryness. The residue is taken up in trichloromethane andworked up by chromatography on silica gel/trichloromethane. Yield 93 mg(91%) in the form of a cherry-red powder, (XLIX), m.p.>300° C., R_(f)(silica gel/trichloromethane): 0.61. - R_(f) (Al₂O₃/trichloromethane):0.77.

Example 4N,N″-Bis(1-hexylheptyl)-N′-benzyl-pyrrolo[2,3,4,5-hik]perylene-3,4:8,9-bis(dicarboximide)(L), Method A

(XLVI), prepared analogously to Example 2a, 100 mg (0.13 mmol), ethanol,10 ml, and potassium hydroxide powder, 11 mg (0.167 mmol), are reactedwith benzyl bromide, 222 mg (1.3 mmol), at 25° C. for 12 hours. Theethanol is then distilled off. The residue of the reaction mixture istaken up in trichloromethane and worked up by chromatography on silicagel/(petroleum ether:trichloromethane) (5:1) and then on silicagel/trichloromethane. Yield 83.0 mg (74%) (L) in the form of a light-redpowder.

Method B:N,N″-Bis(1-hexylheptyl)pyrrolo[2,3,4,5-hik]perylene-3,4;8,9-bis(dicarboximide)(XLVI), prepared analogously to Example 2a, 100 mg (0.130 mmol),tetrahydrofuran, 10 ml, and DBU, 30 mg (0.197 mmol), are reacted withbenzyl bromide, 222 mg (1.30 mmol), at about 25° C. until the startingmaterial can no longer be detected by thin-layer chromatography.Tetrahydrofuran is then distilled off and working up is carried outanalogously to method A. Yield 97 mg (87%) (L), m.p. 134-135° C., R_(f)(silica gel/trichloromethane): 0.62.

Example 5N,N″-Bis(1-hexylheptyl)-N′-ethoxycarbonylmethyl-pyrrolo[2,3,4,5-hik]perylene-3,4;89-bis(dicarboximide)(LI)

(XLVI), prepared analogously to Example 2a, 105 mg (0.137 mmol),tetrahydrofuran, 15 ml, and DBU, 31 mg (0.204 mmol), are reacted withbromoacetic acid ethyl ester, 46 mg (0.277 mmol), at about 25° C. untilthe starting material can no longer be detected by thin-layerchromatography. 2N hydrochloric acid is then added to the batch,followed by as much acetone as required for the excess bromoacetic acidethyl ester to go into solution. The resulting red precipitate isfiltered off, and the filter residue is dried and worked up bychromatography on silica gel/trichloromethane. Yield 95 mg (81%) (LI) inthe form of a bright red powder, m.p. 110-111° C., R_(f) (silicagel/trichloromethane): 0.56.

Example 6aN,N″-Bis(1-hexylheptyl)-N′-acetyl-pyrrolo[2,3,4,5-hik]perylene-3,4;8,9-bis(dicarboximide)(LII)

(XLVI), prepared analogously to Example 2a, 56 mg (0.07 mmol), dissolvedin tetrahydrofuran and DBU, 17 mg (0.11 mmol), are reacted with acetylchloride, 12 mg (0.15 mmol), at 25° C. until the starting material canno longer be detected by thin-layer chromatography. The reaction mixtureis then reacted with water, 50 ml, at 25° C. for 12 hours. The resultingprecipitate is filtered off, and the filter residue is isolated anddried and then worked up by chromatography on silicagel/trichloromethane. Yield 43 mg (73%) (LII) in the form of a brightred powder, m.p.>300° C., R_(f) (silica gel/trichloromethane): 0.62.

Example 6bN,N″-Bis(1-butylpentyl)-N′-acetyl-pyrrolo[2,3,4.5-hik]perylene-3,4:8,9-bis(dicarboximide)(LIII)

(XLVIII), prepared analogously to Example 2b, 48 mg (0.073 mmol),dissolved in tetrahydrofuran, and DBU, 22 mg (0.145 mmol), are reactedwith acetyl chloride, 10 mg (0.128 mmol), at 25° C. until the startingmaterial can no longer be detected by thin-layer chromatography. Thereaction mixture is then reacted with water, 50 ml, at 25° C. for 12hours. The resulting precipitate is filtered off, and the filter residueis isolated and dried and then worked up by chromatography on silicagel/dichloromethane. Yield 35 mg (69%) (LIII) in the form of a brightred powder, m.p.>300° C., R_(f) (silica gel/trichloromethane): 0.23.

Example 7N,N″-Bis(1-hexylheptyl)-N′-benzoyl-pyrrolo[2,3,4,5-hik]perylene-3,4;8,9-bis(dicarboximide)(LIV)

(XLVI), prepared analogously to Example 2a, 80.0 mg (0.104 mmol),dissolved in tetrahydrofuran, and DBU, 25 mg (0.164 mmol), are reactedwith benzoyl chloride, 44 mg (0.314 mmol), at about 25° C. until thestarting material can no longer be detected by thin-layerchromatography. The reaction mixture is then reacted with water, 50 ml,at about 25° C. for about 12 hours. The resulting precipitate isfiltered off. The filter residue is isolated and dried and then workedup by chromatography on silica gel/trichloromethane. Yield 84 mg (92%)(LIV) in the form of a bright red powder, m.p. 181-183° C., R_(f)(silica gel/trichloromethane): 0.51.

Example 81-Bromo-N,N′-bis(1-hexylheptyl)perylene-3,4:9,10-bis(dicarboximide) (LV)

N,N′-Bis(1-hexylheptyl)perylene-3,4:9,10-bis(dicarboximide), preparedanalogously to Chem. Ber. 1988, 121, 225-230), 200 mg (0.265 mmol),dissolved in chlorobenzene, bromine, 1 ml (39.3 mmol), and anhydrouspotassium carbonate, 520 mg (3.77 mmol), are reacted at 60° C. for 24hours. Chlorobenzene is then distilled off, and the distillation residueis worked up by chromatography on silica gel/trichloromethane. Yield 190mg (86%) (LV) in the form of a dark-red powder, m.p. 136-138° C. R_(f)(silica gel/trichloromethane): 0.79.

Example 91-Amino-N,N′-bis(1-hexylheptyl)perylene-3,4:9,10-bis(dicarboximide)(LVI)

Method A: (XLI), prepared analogously to Example 1b,100 mg (0.125 mmol),iron, 50 mg (0.893 mmol), and ethanol (or n-butanol or tetrahydrofuran)are reacted under reflux with concentrated hydrochloric acid, 0.5 ml,until (XLI) can no longer be detected by thin-layer chromatography(about 10-30 minutes). The resulting precipitate is then precipitatedwith water and filtered off. The filter residue is dried and then workedup by chromatography on silica gel/trichloromethane. Yield 78.0 mg (81%)(LVI) in the form of a dark-blue powder

Method B: (XLI), prepared analogously to Example 1b, 20 mg (0.025 mmol),dissolved in tetrahydrofuran, triethylamine, 0.200 ml (1.44 mmol), andpalladium/carbon, 5 mg (5% by weight), are reacted at boilingtemperature for about 30 minutes. Formic acid, 0.040 ml (1.06 mmol) andpalladium/carbon, 5 mg (5% by weight) are then added, and the mixture isreacted at boiling temperature for 25 minutes until (XLI) can no longerbe detected by thin-layer chromatography. Working up is then carried outanalogously to method A. Yield 14 mg (73%) (LVI) in the form of adark-blue powder, m.p. 93-95° C., R_(f) (silica gel/trichloromethane):0.34.

Example 101-Dimethylamino-N,N′-bis(1-hexylheptyl)perylene-3,4:9,10-bis(dicarboximide)(LVII),

Method A: (LVI), prepared analogously to Example 9, 34 mg (0.044 mmol),dissolved in formic acid, 5 ml, and dimethylformamide, 2 ml, are reactedwith formalin solution, 0.5 ml (35% by weight), at 85° C. for 24 hours.Water is then added to the reaction mixture, which is subsequentlyrendered weakly basic with sodium carbonate. The reaction mixture isfiltered and the filter residue is isolated, dried and then worked up bychromatography on silica gel/trichloromethane. Yield: 21 mg (60%) (LVII)

Method B: (LVI), prepared analogously to Example 9, 50 mg (0.065 mmol),dissolved in toluene, potassium hydroxide powder, 15 mg (0.228 mmol) andtriethylbenzylammonium chloride, 5 mg (0.022 mmol), are reacted withmethyl iodide, 0.04 ml (0.642 mmol), at 25° C. for 12 hours. Thereaction mixture is then diluted with the solvent and washed three timeswith water. The organic solvent phase is separated from the aqueousphase and dried over magnesium sulfate, and the solvent is then removedby distillation. Working up is then carried out by chromatography onsilica gel/trichloromethane and then on silica gel/dichloromethane.After elution of the (LVII), there is also obtained as by-product theblueish-green monomethylationproduct,1-methylamino-N,N′-bis(1-hexylheptyl)perylene-3,4:9,10-bis(dicarboximide),(LVIII). Yield 40 mg (77%) (LVII) in the form of a dark-green solid,m.p. 72-74° C., R_(f) (silica gel/trichloromethane): 0.63.

Example 11a1-Amino-N,N′-bis(1-butylpentyl)perylene-3,4:9,10-bis(dicarboximide)(LIX)

(XL), prepared analogously to Example 1a, 100 mg (0.146 mmol), dissolvedin tetrahydrofuran, iron, 50 mg (0.893 mmol), and concentratedhydrochloric acid, 0.5 ml, are reacted at boiling temperature until (XL)can no longer be detected by thin-layer chromatography (after about 15minutes). The reaction mixture is then reacted with water and 2Nhydrochloric acid. The resulting precipitate is filtered off. The filterresidue comprising (LIX) is isolated and dried.

Example 11b1-Dimethylamino-N,N′-bis(1-butylpentyl)perylene-3,4:9,10-bis(dicarboximide)(LX)

(LIX), prepared according to Example 11a, is dissolved indichloromethane, and reacted with potassium hydroxide powder, 30 mg(0.456 mmol), triethylbenzylammonium chloride, 10 mg (0.044 mmol), andmethyl iodide, 0.1 ml (1.61mmol), at 25° C. for 12 hours. The reactionmixture is then diluted with dichloromethane and washed three times withwater. The dichloromethane phase is separated from the aqueous phase anddried over magnesium sulfate, and then the organic solvent is removed bydistillation. Working up is then carried out by chromatography on silicagel/trichloromethane and then on silica gel/dichloromethane. Yield 70 mg(70%) (LX) in the form of a dark-blueish-green product, m.p. 170-172°C., R_(f) (silica gel/trichloromethane): 0.50.

Example 12a 1-Amino-N-(1-hexylheptyl)perylene-3,4:9,10-tetracarboxylicacid 3,4-anhydride-9,10-imide (LXI) and12-amino-N-(1-hexylheptyl)perylene-3,4:9,10-tetracarboxylic acid3,4-anhydride-9.10-imide (LXII)

Method A: A mixture of (XLIII) and (XLIV), prepared according to Example1d, 100 mg (0.162 mmol), is dissolved in 30 ml of tetrahydrofuran, or ina mixture of trichloromethane and ethanol (in a weight ratio of3:1/trichloromethane:ethanol), and reacted with iron, 64 mg (1.14 mmol),and concentrated hydrochloric acid, 0.5 ml, at boiling temperature forabout 30 minutes. After cooling, the reaction mixture is poured into 2Nhydrochloric acid, and acetone is added until a solution is formed (whentetrahydrofuran is used, acetone is not added). The solvent residues arethen distilled off. The residue is filtered. The resulting filterresidue is dried. (LXI) and (LXII) are obtained in the form of adark-blue powder, which is reacted further without purification.

Method B: A mixture of (XLIII) and (XLIV), prepared according to Example1d, 100 mg (0.162 mmol), tetrahydrofuran, 30 ml, triethylamine, 1.3 ml(9.33 mmol), are reacted with palladium/carbon, 15 mg, at boilingtemperature for about 30 minutes. Formic acid, 0.26 ml (6.87 mmol) andpalladium/carbon, 30 mg, are then added to the reaction mixture, andreaction is carried out at boiling temperature for about 30 minutesuntil (XLIII) and (XLIV) can no longer be detected by thin-layerchromatography. The reaction mixture is then cooled to about 25° C. andthe catalyst is removed by filtration. Further working up is carried outas described above, yielding (LXI) and (LXII) in the form of a dark-bluepowder, which is reacted further without purification. M.p. 292-294° C.,R_(f) (silica gel/dichloromethane/2% glacial acetic acid): 0.15-0.40.

Example 12b1-Dimethylamino-N-(1-hexylheptyl)perylene-3,4-anhydride-9,10-dicarboximide(LXIII) and12-dimethylamino-N-(1-hexylheptyl)perylene-3,4-anhydride-9,10-dicarboximide(LXIV)

A mixture of (LXI) and (LXII), prepared according to Example 12a, 58 mg(0.099 mmol), dimethylformamide, 7 ml, formic acid, 2 ml, and formalin,1 ml (37% by weight), are reacted for 24 hours at 105° C. The reactionmixture is then poured into 1N hydrochloric acid. A blueish-greenprecipitate is produced, which is filtered off. The precipitate is thenwashed with water. The precipitate is then dried and worked up, with theexclusion of light, by chromatography on silicagel/trichloromethane/glacial acetic acid (5% by weight). Yield 43 mg(71%) (LXIII) and (LXIV), R_(f) (silica gel/trichloromethane /glacialacetic acid (3% by weight): 0.50; the two isomers are separated bycolumn chromatography on silica gel/trichloromethane/glacial acetic acid(1% by weight);

1st fraction: (LXIII) with R_(f) (silica gel/trichloromethane/glacialacetic acid (1% by weight)): 0.17;

2nd fraction: (LXIV) with R_(f) (silica gel/trichloromethane/glacialacetic acid (1% by weight)): 0.11.

Example 13aN′-Bis(1-butylpentyl)perylo[6,7-cde]-1,2-dithiin-3,4:9,10-bis(dicarboximide)(LXV) andN,N′-bis(1-butylpentyl)perylo[1,12-bcd]-thionhene-3,4:9,10-bis(dicarboximide)(LXVI)

Sulfur, 20 mg (0.63 mmol), is dissolved in N,N′-dimethylformamide, 10ml, at 80-90° C., and then reacted with1-nitro-N,N′-bis(1-butylpentyl)perylene-3,4:9,10-bis-(dicarboximide),(XL), prepared according to Example 1a, 100 mg (0.15 mmol), preparedanalogously to Example 1a, under an argon atmosphere at 120-130° C. for10 hours until1-nitro-N,N′-bis(1-butylpentyl)perylene-3,4:9,10-bis(dicarboximide) canno longer be detected by thin-layer chromatography. The reaction mixtureis then poured into a mixture of two parts water and one part 2Nhydrochloric acid, about 100 ml. The resulting dark precipitate isfiltered off and the filter residue is washed with water. The filterresidue is then dried at 70° C. and by chromatography on silicagel/trichloromethane, and then the excess sulfur is removed fromfraction 1 on silica gel/petroleum ether (about 2 liters). Elution withtrichloromethane is then carried out.

1st fraction: yield 42 mg (42%) (LXV), m.p.>300° C.; R_(f) (silicagel/trichloromethane): 0.63;

2nd fraction: yield 49 mg (47%) (LXVI) in the form of a bright orangepowder, m.p.>300° C., R_(f) (silica gel/trichloromethane): 0.54.

Example 13bN,N′-Bis(1-hexylheptyl)perylo[6,7-cde]-1,2-dithiin-3,4:9,10-bis(dicarboximide)(LXVII) andN,N′-bis(1-hexylheptyl)perylo[1,12-bcd]-thiophene-3,4:9,10-bis(dicarboximide)(LXVIII)

Sulfur, 160 mg (4.9 mmol), is dissolved in N-methylpyrrolidone, 12 ml,at 70° C., and reacted with1-nitro-N,N′-bis(1-hexylheptyl)perylene-3,4:9,10-tetracarboxylic acid3,4:9,10-bis(dicarboximide), (XLI), 50 mg (0.62 mmol), preparedanalogously to Example 1b, under argon at 130° C. for 75 minutes. Thereaction mixture is then poured into water, 150 ml. The resulting darkprecipitate is filtered off and the filter residue is then washed withwater. The residue is then dried at 70° C. and worked up bychromatography on silica gel/trichloromethane, and then the excesssulfur is removed from fraction on silica gel/petroleum ether (about 2liters). Working up is then carried out on silica gel/trichloromethane.

1st fraction: yield 130 mg (25%) (LXVII), m.p. 158-160° C., R_(f)(silica gel/trichloromethane): 0.72;

2nd fraction: yield 295 mg (60%) (LXVIII) in the form of a bright orangepowder, m.p. 263-265° C., R_(f) (silica gel/trichloromethane): 0.67.

Example 13cBis(2,5-di-tert-butylphenyl)-perylo[6.7-cde]-1.2-dithiin-3,4:9,10-bis(dicarboximide)(LXIX) andN,N′-bis(2,5-di-tert-butylphenyl)-perylo[1,12-bcd]thiophene-3,4:9,10-bis-(dicarboxidmide)(LXX)

Sulfur, 24.0 mg (0.750 mmol) is dissolved in N,N′-dimethylformamide, 10ml, at 90° C. and reacted1-nitro-N,N′-bis(2,5-di-tert-butylphenyl)perylene-3,4:9,10-bis(dicarboximide),(XLII), (prepared as in Example 1c) 100 mg (0.123 mmol), under argon at120° C. for 17 hours until1-nitro-N,N′-bis(2,5-di-tert-butylphenyl)perylene-3,4:9,10-(dicarboximide) can no longer be detected by thin-layer chromatography.The reaction mixture is then poured into a mixture of two parts waterand one part 2N hydrochloric acid, about 100 ml. The resulting darkprecipitate is filtered off, and then the filter residue is washed withwater. The residue is then dried at 70° C. and worked up bychromatography.

1st fraction: yield 56 mg (55%) (LXIX), m.p.>300° C., R_(f) (silica gel,trichloromethane): 0.36;

2nd fraction: yield 29 mg (30%) (LXX) in the form of a bright orangepowder, m.p.>300° C.; R_(f) (silica gel/trichloromethane): 0.32.

Example 14aN,N′-Bis(1-hexylheptyl)benzoperylene-1′,2′:3,4:9,10-hexacarboxylic acid1′,2′-anhydride-3,4:9,10-bis(dicarboximide) (LXXI)

N,N′-Bis(1-hexylheptyl)perylene-3,4:9,10-bis(dicarboximide), preparedanalogously to Chem. Ber.—121, 225-230, 1.50 g, (1.99 mmol), moltenmaleic acid anhydride (at 95° C.) and a few milliliters of acetone, areheated with chloranil, 970 mg (3.98 mmol) at 125° C. for 4 days. Thereaction mixture is then cooled to about 30-40° C., poured into amixture of acetone and 2N hydrochloric acid, 250 ml, and reacted at 25°C. for 12 hours. The reaction mixture is then filtered, and the filterresidue is washed several times with water and then dried. The driedfilter residue is then dissolved in trichloromethane and worked up bychromatography on silica gel/trichloromethane. The first fraction elutedis the excess chloranil andN,N′-bis(1-hexylheptyl)perylene-3,4:9,10-bis(dicarboximide).Chromatography is then continued with a mixture of trichloromethane andglacial acetic acid (1-5% by weight) and (LXXI) is eluted. Yield 1.20 g(71%) (LXXI) in the form of a dark-yellow powder, m.p.>200° C.(decomp.), R_(f) (silica gel/trichloromethane/glacial acetic acid 10:1):0.81.

Example 14bN,N′-Bis(1-butylpentyl)benzoperylene-1′,2′:3,4:9,10-hexacarboxylic acid1′,2′-anhydride-3,4:9,10-bis(dicarboximide) (LXXII):

N,N′-Bis(1-butylpentyl)perylene-3,4:9,10-bis(dicarboximide) (prepared asabove), 500 mg (0.779 mmol), molten maleic acid anhydride (at 95° C.)and a few milliliters of acetone are reacted with chloranil, 380 mg(1.56 mmol), and worked up as in Example 14a. Yield 450 mg (77%) (LXXII)in the form of a bright orange powder, m.p.>300° C., R_(f) (silicagel/trichloromethane): 0.00-0.12.

Example 14cN,N′-Bis(2,5-di-tert-butylphenyl)benzoperylene-1′,2′:3,4:9,10-hexacarboxaticacid 1′,2′-anhydride-3,4:9,10-bis(dicarboximide) (LXXIII)

N,N′-Bis(2,5-di-tert-butylphenyl)perylene-3,4:9,10-bis(dicarboximide)(prepared as above), 300 mg (at 95° C.) and a few milliliters of acetoneare reacted with chloranil, 240 mg (0.984 mmol), as in Example 14a, andworked up. The reaction mixture is purified by chromatography on silicagel/trichloromethane/ethanol (10% by weight) and then on silicagel/trichloromethane/glacial acetic acid (10% by weight). Yield 230 mg(67%) (LXXIII) in the form of a dark-yellow powder, m.p.>300° C., R_(f)(silica gel/trichloromethane/ethanol (10% by weight)): 0.00-0.16.

Example 15aN,N′-Bis(1-hexylheptyl)benzoperylene-1′,2′:3,4:9,10-hexacarboxylic acid1′,2-bisethoxycarbonyl-3,4:9,10-bis(dicarboximide) (LXXIV)

(LXXI), 110 mg (0.127 mmol), prepared analogously to Example 14a,dissolved in tetrahydrofuran, and DBU, 60 mg (0.395 mmol), are reactedwith ethyl iodide, 100 mg (0.641 mmol), at 25° C. for 12 hours. Thereaction mixture is then poured into water, 150 ml, then rendered weaklyacidic with 2N hydrochloric acid and reacted at 25° C. for 12 hours. Thereaction mixture is filtered, and the filter residue is dried and thenworked up by chromatography on silica gel/trichloromethane. Yield 100 mg(85%) (LXXIV) in the form of a bright orange powder, m.p.: 273-275° C.,R_(f) (silica gel/trichloromethane): 0.65.

Example 15bN,N′-Bis(2,5-di-tert-butylphenyl)benzoperylene-1′,2′:3,4:9,10-hexacarboxylicacid 1′,2′-bisethoxycarbonyl-3,4:9,10-bis(dicarboximide) (LXXV)

(LXXIII), 50 mg (0.060 mmol), prepared analogously to Example 14c,dissolved in tetrahydrofuran, and DBU, 35 mg (0.23 mmol), are reactedwith ethyl iodide, 45 mg (0.29 mmol) as in Example 15a and worked up.Purification by chromatography is carried out on silicagel/trichloromethane/ethanol (3% by weight), yield: 41 mg (78%) (LXXV)in the form of an egg-yolk-yellow powder, m.p.>300° C., R_(f) (silicagel/trichloromethane): 0.24.

Example 16N,N″-Bis(1-hexylheptyl)-N′-cyclohexyl-benzoperylene-1′,2′:3,4:9,10-hexacarboxylicacid 1′,2′:3,4:9,10-tris(dicarboximide) (LXXVI)

(LXXI), 100 mg (0.118 mmol), prepared analogously to Example 14a,cyclohexylamine, 114 mg (1.15 mmol), and quinoline, 10 ml, are reactedat 160° C. for 6 hours. The reaction mixture is then poured into 2Nhydrochloric acid, 100 ml, and stirred for a few hours at about 25° C.The resulting precipitate is then filtered off and the filter residue isdried and worked up by chromatography on silica gel/trichloromethane.Yield: 71 mg (66%) (LXXVI) in the form of an orange-yellow powder,m.p.>300° C., R_(f) (silica gel/trichloromethane): 0.63.

Example 17

N,N″-Bis(1-hexylheptyl)-N′-2,5-di-tert-butylphenylbenzoperylene-1′,2′:3,4:9,10-hexacarboxylicacid 1′,2′:3,4:9,10-tris(dicarboximide) (LXXVII)

(LXXI), prepared analogously to Example 14a, 60.0 mg (0.0710 mmol),2,5-di-tert-butylaniline, 100 mg (0.488 mmol), and DCC, 75 mg (0.364mmol), are boiled with trifluoroacetic acid (1drop) at boilingtemperature for about 24 hours. The reaction mixture is then dilutedwith trichloromethane, and subsequently washed several times with water.The organic solvent phase is separated from the aqueous phase,concentrated in vacuo and purified by chromatography on silicagel/trichloromethane, and then aluminium oxide neutral/petroleumether/3% trichloromethane). Yield: 50 mg (70%; yield 50% after 4 days'reaction time when only DCC or only trifluoroacetic acid is used) in theform of a bright-yellow solid, m.p.: 285-287° C., R_(f) (silicagel/trichloromethane): 0.66.

Example 18aN,N′-Bis(1-hexylheptyl)benzoperylene-3,4:9,10-tetracarboxylic acid3,4:9,10-bis(dicarboximide) (LXXVIII)

(LXXI), prepared analogously to Example 14a, 50 mg (0.060 mmol) andcopper(I) oxide, 40 mg (0.28 mmol), in quinoline are reacted under anargon atmosphere at 180° C. for 4 hours. The reaction mixture is thencooled to about 25-30° C., poured into 2N hydrochloric acid, and treatedat about 25-30° C. for 12 hours. The resulting precipitate is filteredoff with suction, dried and worked up by chromatography on silicagel/trichloromethane. Yield: 16 mg (36%) (LXXVIII) in the form of ayellow- to orange-coloured powder, m.p. 289-291° C., R_(f) (silicagel/trichloromethane): 0.82.

Example 18bN,N′-Bis(1-hexylheptyl)benzoperylene-3,4:9,10-tetracarboxylic acid3,4:9,10-bis(dicarboximide)

(LXXVIII): (LXXI), prepared analogously to Example 14a, 50 mg (0.060mmol), and copper powder, 40 mg (0.64 mmol) in 3-picoline are reactedunder an argon atmosphere at boiling temperature for 3 days. Thereaction mixture is then cooled to about 25-30° C., poured into 2Nhydrochloric acid, and treated at 25-30° C. for 12 hours. The resultingprecipitate is filtered off with suction, dried and worked up bychromatography on silica gel/trichloromethane. Yield: 21.3 mg (48%)(LXXVIII) in the form of a yellow to orange powder, m.p.: 289-291° C.,R_(f) (silica gel/trichloromethane): 0.82.

Example 19aN,N′-Bis(1-hexylheptyl)-2-phenyl-benzo[4.10]anthrar[1,9,8cdef][1,2,4]triazolo[1,2-a]cinnoline-1,3-dione-5,6:11,12-bis(dicarboximide) (LXXIX)

N,N′-Bis(1-hexylheptyl)-perylene-3,4:9,10-tetracarboxylic acid3,4:9,10-bis(dicarboximide) (prepared as above), 100 mg, (0.133 mmol),4-phenyl-1,2,4-triazoline-3,5-dione, 180 mg (1.03 mmol) and chloranil,32.5 mg (0.133 mmol), are reacted in dried toluene for 24 hours atboiling temperature. Toluene is then removed from the reaction mixtureby distillation, and the residue is worked up by chromatography onsilica gel/trichloromethane and then on silica gel/dichloromethane.Yield: 32 mg (25%) (LXXIX) in the form of a green solid, m.p.>300° C.,R_(f) (silica gel/trichloromethane): 0.32, R_(f) (silicagel/dichloromethane): 0.56.

Example 19bN,N′-Bis(1-hexylheptyl)-2-phenyl-benzo[4,10]anthra[1,9,8-cdef][1,2,4]triazolo[1,2-a]cinnoline-1,3-dione-5,6:11,12-bis(dicarboximide)(LXXIX) or (XVI)

N,N′-Bis(1-hexylheptyl)perylene-3,4:9,10-tetracarboxylic acid3,4:9,10-bis(dicarboximide) (prepared as above), 500 mg (0.665 mmol),and para-chloranil, 163 mg (0.665 mmol), in dried toluene are reactedwith 4-phenyl-1,2,4-triazoline-3,5-dione, in 6 weight-equivalentportions each of 139 mg (1.11 mmol) at time intervals of about 2 hoursat boiling temperature, and then heated at boiling temperature for afurther 12 hours. Toluene is then removed from the reaction mixture bydistillation and the residue is worked up by chromatography on silicagel/trichloromethane and then on silica gel/dichloromethane. Yield.: 252mg (41%) (LXXIX); or in the form of a blue compound (XVI), wherein R¹and R² are N-1-hexylheptyl, and R⁴ is phenyl, R_(f)=0.16 (CHCI₃).

Example 2011,12-Diaza-11,12-dihydrobenzo[ghi]-perylene-2,3,8,9,11,12-hexacarboxylicacid 2,3:8,9-bis(1-hexylheptylimide)-11,12-diisopropyl ester (LXXX)11,12-diazabenzo [ghi]perylene-2,3,8,9-tetracarboxylic acid2,3:8,9-bis(1-hexylheptylimide) (LXXXI)

N,N′-Bis(1-hexylheptyl)perylene-3,4:9,10-tetracarboxylic acid3,4:9,10-bis(dicarboximide) (prepared as above), 100 mg (0.133 mmol),dissolved in 5 ml of toluene, 5.05 g (25 mmol) of diisopropylazodicarboxylate and 64 m (0.26 mmol) of para-chloranil are reacted at140° C. for a week. Working up is then carried out by chromatography onsilica gel/trichloromethane. (LXXX) and (LXXXI) are identified in themass spectrum by the mass unit: (LXXX) of 955 u, and (LXXXI) of 781 u.

Example 2111,12-Diaza-11,12-dihydrocoronene-2,3,5,6,8,9,11,12-octacarboxylic acid5,6-anhydride-2,3:8,9-bis (1-hexylheptylimide)-11,12-phenylimide(LXXXII)

(LXXIX), prepared as in Example 19a, 250 mg (0.27 mmol), molten maleicacid anhydride, 10 g (102 mmol), and para-chloranil, 132 mg (0.54 mmol),are reacted for four weeks at 125° C. with a small amount oftrichloromethane for flushing back evaporated maleic acid anhydride.Working up is carried out by column chromatography on silica gel withdichloromethane to remove the starting materials, and then elution iscarried out with dichloromethane/5% glacial acetic acid. Yield: 57%,R_(f) value: 0.0-0.6 (CH₂Cl₂).

Example 22

0.5 g (0.66 mmol) ofN,N′-bis(1-hexylheptyl)perylene-3,4:9,10-bis(dicarboximide) and 0.32 g(1.32 mmol) of p-chloranil are added to 10 g of moltenN-phenylmaleimide. A small amount of chloroform is added to theresulting mixture and heating is carried out for three days at 120° C. Asmall amount of chloroform is then added and the product is precipitatedwith a large amount of methanol. Filtration yields 575 mg (94%) of thedesired product (formula IXb, R⁴=phenyl, R¹=R²=1-hexylheptyl), R_(f)value (CHCl₃)=0.8.

Example 23N,N′-Bis(1-hexylheptyl)benzo[ghi]perylene-2,3,8,9,11,12-hexacarboxylicacid 2,3;8,9-bis(dicarboximide)-11,12-dicarboximide (IXa)

1.00 g (1.17 mmol) ofN,N′-bis(1-hexylheptyl)benzo[ghi]perylene-2,3,8,9,11,12-hexacarboxylicacid 2,3;8,9-bis(dicarboximide)-11,12-anhydride is mixed with 6 g ofimidazole. 4.57 g (47.16 mmol) of finely pulverised amidosulfuric acidare then added, and the batch is stirred for four hours under an argonatmosphere in an oil bath at an oil-bath temperature of 160° C. After afew minutes, perceptible reaction commences, the batch quiterecognisably changing from dark yellow to brown. After the reaction iscomplete, the batch is left to cool slowly, and is flushed out of theflask with 400 ml of 2N hydrochloric acid and stirred further for aboutone hour at room temperature. The precipitate is filtered off withsuction, then washed with a further 200 ml of twice-distilled water anddried overnight at 120° C. in a drying cabinet. The resulting crudeproduct is dissolved in a small amount of chloroform, applied to asilica gel column and then chromatographed with the eluant mixturechloroform/acetone (15:1). In that process, after separation of ayellowish-green-fluorescent first running, the product is obtained inthe form of broad, reddish-yellow bands. For further purification, thedye is chromatographed again over a neutral aluminium oxide with theeluant mixture chloroform/acetone (15:1). The resulting solution isconcentrated and, after cooling, the dye is precipitated slowly withmethanol. The resulting precipitate is filtered off and dried at 80° C.in an atmosphere under reduced pressure, yielding 0.83 (84%) of alight-yellow bright powder having a melting point of>260° C.(decomposition). R_(f) (chloroform/acetone 15:1): 0.74. Fluorescence(chloroform, corrected)λ_(max.) (rel. intensity)=481nm (0.99), 508(1.00), 550 (0.56).

Fluorescence quantum yield (chloroform): φ=49%, based onperylene-3,4:9,10-tetracarboxylic acid tetramethyl ester (100%) asstandard.

What is claimed:
 1. A nucleus-extended perylenebisimide of generalformula (I)

wherein R¹ and R² are each independently of the other secondary alkylradical of the formula 1-(C₁-C₉alkyl)-C₂-C₁₀alkyl, C₁-C₂₄cycloalkyl, orC₆-C₁₀aryl, and A¹ is —S—, —S—S—, -CH═CH—, R³OOC—C(—)═C(—)—COOR³,—N═N—or —N(R⁴)—, or a linkage selected from the group consisting of theorganic radicals of formulae (III), (IV), (V), (VI) and (VII)

 wherein R³ is hydrogen, C₁-C₂₄ alkyl or C₁-C₂₄cycloalkyl, and R⁴ isunsubstituted or substituted C₁-C₂₄alkyl, C₁-C₂₄cycloalkyl, phenyl,benzyl, -CO-C₁-C₄alkyl, -CO-C₆H₅ or C₁-C₄alkylcarboxylic acid(C₁-C₄alkyl) ester. with the proviso that when Al is —s—, then either R₁or R₂ is not a phenyl group.
 2. A process for the preparation ofperylenebisimides (I) according to claim 1, wherein A¹ is A⁴, wherein A⁴is a linkage selected from the group consisting of the organic radicalsof formulae (III), (IV), (V), (VII) and —N═N—, by Diels-Alder reactionof a diene with a dienophile at elevated temperaure, wherein thereinthere are reacted, as diene, a perylenebisimide of formula (XXI)

and, as dienophile, a compound selected from the group consisting of thecompounds of formulae (XXII), (XXIII) and (XXIV)


3. A method for coloring high molecular weight organic materialcomprising incorporating at least one perylene according claim 1 intosaid high molecular organic material, wherein said high molecular weightorganic material is a polymeric material.
 4. A method according to claim3 wherein the high molecular weight organic material is selected fromthe group consisting of polyvinyl chloride, cellulose acetate,polycarbonate, polyamide, polyurethane, polyimide, polybenzimidazole,melamine resin, silicone, polyester, polyether, polystyrene, polymethylmethacrylate, polyethylene, polypropylene, polyvinyl acetate,polyacrylonitrile, polybutadiene, polychlorobutadiene, polyisoprene, andcopolymers and mixtures thereof.
 5. A method for preparing a dyecomposition comprising incorporating at least one perylene accordingclaim 1 into a homogenous solution suitable for use as a dye.
 6. Amethod for preparing a coating composition comprising incorporating atleast one perylene according to claim 1 into a homogenous solutionsuitable for use as a coating for a substrate.
 7. A method according toclaim 5, wherein the coating composition is selected from the groupconsisting of a paint product, lacquer, paper dyes or printing ink.